Formulation of the LCAS MS SCF method within the Gaussian basis set

Within the presented LCAS MS (linear combination of atomic spinors–molecular spinors) SCF formalism both large and small components of the spinor radial parts have been expanded within the Gaussian basis set. The respective expressions for matrix elements as well as for one- and two-electron integrals are given.     

H-bonding dependent structures of (NH4+)3H+(SO4 2-)2. Mechanisms of phase transitions

The role of different H-bonds in phases II, III, IV, and V of triammonium hydrogen disulfate, (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2), has been studied by X-ray diffraction and (1)H solid-state MAS NMR. The proper space group for phase II is C2/c, for phases III and IV is P2/n, and for phase V is P onemacr;. The structures of phases III and IV seem to be the same. The hydrogen atom participating in the O(-)-H(+).O(-) H-bond in phase II of (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2) at room temperature is split at two positions around the center of the crucial O(-)-H(+).O(-) H-bonding, joining two SO(4)(2)(-) tetrahedra. With decreasing temperature, it becomes localized at one of the oxygen atoms. Further cooling causes additional differentiation of possibly equivalent sulfate dimers. The NH(4)(+) ions participate mainly in bifurcated H-bonds with two oxygen atoms from sulfate anions. On cooling, the major contribution of the bifurcated H-bond becomes stronger, whereas the minor one becomes weaker. This is coupled with rotation of sulfate ions. In all the phases of (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2), some additional, weak but significant, reflections are observed. They are located between the layers of the reciprocal lattice, suggesting possible modulation of the host (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2) structure(s). According to (1)H MAS NMR obtained for phases II and III, the nature of the acidic proton disorder is dynamic, and localization of the proton takes place in a broader range of temperatures, as can be expected from the X-ray diffraction data.     

Comparison of the differential isosteric adsorption enthalpies and entropies calculated from chromatographic data

The differential isosteric enthalpies, -deltaH(ads), and entropies, -deltaS(ads), of adsorption were calculated taking the retention times of the peak maxima and the centres of gravity of peaks into account and compared with the results obtained from the adsorption second virial coefficients. A mathematical link between the -deltaH(ads) and -deltaS(ads) magnitudes and experimental data was derived through the Antoine-type equation which enables the -deltaH(ads) and -deltaS(ads) magnitudes to be found from adsorption second virial coefficients, B2S, calculated on the basis of chromatographically determined adsorption isotherm data. The virial coefficients were calculated employing the values of the Tóth and Unilan equation parameters. There are no significant differences to be found between the isosteric enthalpies obtained, whereas the values of the adsorption entropies were the highest for the centre of peak gravity data.     

RESOLUTION OF TWO EMISSION SPECTRA FOR TRYPTOPHAN USING FREQUENCY-DOMAIN PHASE-MODULATION SPECTRA

We describe a novel application of frequency-domain fluorometry which allows resolution of the decay times and emission spectra of samples which display multi-exponential decay kinetics. This method does not require any previous knowledge about the decay times or any assumptions about the shape of the emission spectra. We record the wavelength-dependent phase angles and modulations (phase angle and modulation spectra) using a number of light modulation frequencies. The data is analyzed by non-linear least-squares to recover the emission spectra and their associated decay times. Phase and modulation spectra (PM Spec) were used to recover the emission spectra associated with the two decay times of tryptophan at pH = 7 (0.54 and 3.44 ns). The emission spectra of these components are centered at 340 and 355 nm, respectively, with the amplitude of the 0.54 ns component contributing 6% to the total emission. These results are in agreement with previous time-resolved studies by Szabo and Rayner [J. Am. Chem. Soc. 102, 554-563 (1980)]. Control experiments were performed on mixtures of N-acetyl-L-tryptophanamide (NATA) and PPD, which demonstrate our ability to recover the spectra and decay times from two component mixtures. NATA itself displayed a single decay time and only one emission spectrum.     

Ghost orbitals in semiempirical methods. Estimation of basis set superposition error

Based on the all-valence ZDO SCF approximation a procedure for estimating the basis set superposition error (BSSE ) in semiempirical CNDO /INDO methods has been proposed. The results of the calculation show that the BSSE effect may improve the results obtained from the standard CNDO /INDO supermolecule calculation. The estimated BSSE effect enables one to explain some recently reported artificial structures for water and ethylene dimers.     

Uniformly non-l n (1) Musielak-Orlicz sequence spaces

We give a necessary and sufficient condition for the uniformly non-l _n ⁽¹⁾ property of Musielak-Orlicz sequence spacesl ^Φ generated by a sequence Φ=(ϕ_n:n⩾l) of finite Orlicz functions such that for eachn∈ℕ. As a result, forn ₀⩾2, there exist spacesl ^Φ which are only uniformly non-l _n ⁽¹⁾ forn⩾n ₀. Moreover we obtain a characterization of uniformly non-l _n ⁽¹⁾ and reflexive Orlicz sequence spaces over a wide class of purely atomic measures and of uniformly non-l _n ⁽¹⁾ Nakano sequence spaces. This extends a result of Luxemburg in [19]. Submitted in memory of Professor W. Orlicz     

Fine tuning the structure of the Cu2+ complex with the prion protein chicken repeat by proline isomerization

The interaction between the single hexarepeat unit of chicken prion protein [ChPrP(54-59)] and Cu(II) was investigated by NMR, finding different coordination modes for the trans/trans and cis/trans isomers.     

Complexes of heteroscorpionate trispyrazolylborate ligands. Part VI. Carboxylate induced conversion of mono-ligand Tp′M(L) into bis-ligand Tp′2M complexes (M=Co(II) and Cu(II))

A series of homoleptic complexes of hexacoordinate cobalt(II) and copper(II) complexes with 3,5-disubstituted homo- and heteroscorpionate tris(pyrazolyl)borate anionic ligands (Tp′) were synthesized, i.e. bis[hydrotris(3-phenyl,5-methylpyrazol-1-yl)borato]cobalt(II), bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) and bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]copper(II) and their structures were elucidated crystallographically. The complexes were also formed spontaneously during attempted metathesis of the corresponding Tp′M(NCS) complexes into Tp′M(OOCCH(OH)CH₃) complexes. In the case of the analogous conversion applied for the thiocyanato [hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3,5-dimethylpyrazol-1-yl)boratocobalt(II) complex with sodium carboxylates (lactate, pyruvate and 2-hydroxybutyrate), the cross-transfer of pyrazolyl residues between starting anionic ligands was observed resulting in formation of bis-ligand homo- and heteroleptic Tp′CoTp″ complexes, where Tp′, Tp″ were tris(pyrazolyl)borates composed of n 3(5)-phenyl,5(3)-methylpyrazolyl and (3−n) 3,5-dimethylpyrazolyl residues (n=0–3) identified by mass spectrometry. Metathesis of thiocyanate in thiocyanato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) into pyruvate led to the isolation of stable the pyruvato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) complex, the structure of which was determined crystallographically. The Tp′ ligands are η³ coordinated to metal ions in every case, whereas the pyruvate anion is coordinated through carboxylate and carbonyl oxygen atoms to the cobalt center. Two rotational isomers distinguishable by ¹H NMR spectroscopy for the hexacoordinate bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) complex were detected in solution.     

微纳尺度光纤布拉格光栅折射率传感的理论研究

亚波长直径微纳光纤强倏逝场传输的光学特性,使其对周围介质折射率的变化具有极高的灵敏度.本文提出一种基于微纳尺度光纤布拉格光栅(MNFBG)的折射率传感器,结合微纳光纤倏逝场传输和光纤布拉格光栅(FBG)强波长选择的特性来实现高精度折射率传感,对其制备可行性进行了讨论.论文中对MNFBG折射率传感机理进行了深入的理论分析,并使用OptiGrating软件进行了数值模拟,模拟数据显示MNFBG折射率测量的灵敏度随着光纤半径的减小而增加,其中光纤半径为400 nm的MNFBG灵敏度可达到993 nm/RIU,相比于包层蚀刻的FBG灵敏度增加了170倍,说明MNFBG对发展微型化、高灵敏度折射率传感器具有良好的应用前景. 关键词： 微纳光纤 光纤布拉格光栅 折射率传感